Heat transfer printing sheet

ABSTRACT

A heat transfer printing sheet wherein a pattern comprising a basic dye having a poor heat transferable property, an oxidizing agent having the property of increasing the heat transferable property of the basic dye and a binder is formed on a base support sheet and a process for heat transfer printing wherein the above heat transfer printing sheet is brought into contact with a material to be transfer printed with the surface of the heat transfer printing sheet which contains said pattern, and the whole is heated under a pressure to effect the transfer of the basic dye but not of the oxidizing agent and the binder and then the heat transfer printing sheet is peeled off from the latter to transfer print the optional pattern onto said material. The pattern can comprise two layers in which one comprises the basic dye and the binder and other comprises the oxidizing agent and the binder. The base support sheet can be formed of a resin film through which the basic dye cannot be passed when the heat transfer printing is not carried out. The pattern can be coated with a resin film through which the basic dye cannot be passed when the heat transfer printing is not carried out, but can be passed when the heat transfer printing is carried out.

United States Patent [191 Mizuno et a1.

[ Nov. 25, 1975 HEAT TRANSFER PRINTING SHEET [75] Inventors: ShogoMizuno, Toride; Sumio lshii,

Inaki, both of Japan [30] Foreign Application Priority Data May 19, 1972Japan 47-49136 Mar. 20, 1973 Japan 48-31440 [52] U.S. C1. 428/467;8/2.5; 101/470; 428/497; 428/498; 428/500; 428/514; 428/537; 428/538[51] Int. Cl. 1341M 5/26; B41M 1/12; B41M 01/26; D06P 01/42 [58] Fieldof Search 8/25; l17/36.8, 36.9, 117/38, 45, l5, 12; 101/467, 470, 471,473

[56] References Cited UNITED STATES PATENTS 2,401,755 6/1946 Griffin eta1. 117/15 X 2,663,654 12/1953 Miller et a1. ll7/36.8

2,770,534 11/1956 Marx, Jr. 8/25 X 3,108,896 10/1963 Owen l17/36.8

3,505,956 4/1970 Pizzi 101/473 X 3,647,503 3/1972 Mizutani et a1. 117/38X 3,649,332 3/1972 Dybvig 8/25 x FOREIGN PATENTS OR APPLICATIONS 882,20811/1961 United Kingdom 117/15 OTHER PUBLICATIONS American DyestuffReporter, Vol. 54, No. 1, Jan. 4,

1965. l-Iowes Publishing Co., Inc., New York, N.Y., pp. 26-38.

Primary Examiner-Charles E. Van Horn Assistant Examiner-Thomas BokanAttorney, Agent, or Firm-Stewart and Kolasch, Ltd.

[5 7] ABSTRACT A heat transfer printing sheet wherein a patterncomprising a basic dye having a poor heat transferable property, anoxidizing agent having the property of increasing the heat transferableproperty of the basic dye and a binder is formed on a base support sheetand a process for heat transfer printing wherein the above heat transferprinting sheet is brought into contact with a material to be transferprinted with the surface of the heat transfer printing sheet whichcontains said pattern, and the whole is heated under a pressure toeffect the transfer of the basic dye but not of the oxidizing agent andthe binder and then the heat transfer printing sheet is peeled off fromthe latter to transfer print the optional pattern onto said material.The pattern can comprise two layers in which one comprises the basic dyeand the binder and other comprises the oxidizing agent and the binder.The base support sheet can be formed of a resin film through which thebasic dye cannot be passed when the heat transfer printing is notcarried out. The pattern can be coated with a resin film through whichthe basic dye cannot be passed when the heat transfer printing is notcarried out, but can be passed when the heat transfer printing iscarried out.

18 Claims, No Drawings HEAT TRANSFER PRINTING SHEET The presentinvention relates to a heat transfer printing sheet and heat transferprinting method using the same, and more particularly relates to a heattransfer printing sheet and heat transfer printing method using the samewherein beautiful transfer printed articles have a clear color tone andgood color fastness can be produced by temporarily increasing the heattransferability of a coloring agent without damage of tinting strengthof the latter.

Various processes for coloring various materials have been hithertodeveloped and proposed, and among them there are such sublimitingtransfer printing methods as described in US. Pat. No. 3,363,557 andBritish Pat. No. 951,987.

Normally these processes are such as to form any patterns on any supportby using ink composition containing as a main ingredient a coloringagent such as a disperse and oil-soluble dye which are rich in asublimating property and then to bring a material to be transfer printedinto contact with the pattern-formed surface of the sheet and to heatthem together, and thereby the material to be transfer printed iscolored by transfer printing the above-mentioned patterns on the formerdue to the sublimation of the coloring agent by heat. Therefore, theseprocesses have very superior advantages that the coloring can beeffected in a dry-heat state because printing, steaming or washing stepscan be omitted.

Since, the sublimating transfer printing method has the under-mentioneddisadvantages, however, the development has been greatly obstructed inspite of the presence of the above-mentioned superior advantages.

In the sublimating transfer printing method, namely, dispense dyeshaving the sublimating property have been generally used as the coloringagent and as a result of the kind of material to be transfer printed isconsiderably limited.

The fiber which can be colored with the disperse dye is principally allsynthetic fibers including polyester fibers and triacetate fibers, butthe fiber which can be substantially used is only the polyester fiber inthe consideration of various fastnesses such as heat resistance andwashing resistance and further the heat resistance of the fiber itselfat the dyeing step. Therefore, the disperse dyes substantially cannot beapplied for other synthetic fibers, and particularly the disperse dyecan not be absolutely applied for the dying of natural fibers such assilk, wool and cotton due to the absence of dyeability thereof bydisperse dye.

Accordingly, if the range of kind of the material to be transfer printedis enlarged for the application in the sublimating transfer printingmethod, coloring agents other than the disperse dyes must be necessarilyused, but these coloring agents substantially do not have aheat-sublimating property Even if a heat-transfer printing is effectedby using these coloring agents it is difficult to obtain a verybeautiful transfer printed product having a sufficient commodity value.Furthermore, said sublimating transfer printing method has anindispensable disadvantage that the fastness of the sublimation printingis considerably poor.

Namely, since sublimation transfer printing method is the processwherein the coloring is effected by diffusing and penetrating a dispersedye having a high sublimatability into fibers, the dye is againactivated to re- 2 versely sublimate when the colored base material isagain subjected to heating and as a result there are disadvantages thatthe colored pattern is degraded and the coloring agent contaminatesother materialv The object of the present invention is to provide a heattransfer printing sheet which can produce a beautiful transfer printedarticle having very clear color tone and various fastness properties.

Another object of the present invention is to provide a heat transferprinting sheet which can produce a transfer printed article having asuperior fastness for sublimation.

A further object of the present invention is to provide a heat transferprinting sheet which can enlarge the range for the application of thematerial to be transfer printed.

As a result of our investigation in order to attain the above-mentionedobjects we have found that when a basic dye having a poor transferableproperty based upon the phenomena such as heat-melting, -evaporation or-sublimation is acted with an oxidizing agent, the heat-transferabilityof the basic dye can be temporarily increased by the occurance of changeof phenomena such as heat-melting, -evaporation or -sublimation due toheating, and thereby the range for the application of the material to betransfer printed can be enlarged, after the above-mentioned coloringagent in transferred onto the material to be transfer printed the basicdye is returned to the original basic dye having superior fastnessproperties and as a result a beautiful transfer printed article havingvery clear tone and various fastness properties can be obtained.

According to one feature of the present invention, therefore, there isprovided a heat transfer printing sheet characterized in that a patterncomprising a basic dye having a poor heat transferability property, anoxidizing agent having a property of increasing the heat transferableproperty thereof and a binder is formed on a base support sheet.

According to another feature of the present invention, furthermore,there is provided a process for heat transferability printingcharacterized in that a heat transfer printing sheet which has formedthereon a pattern comprising a basic dye having a poor heat transferableproperty, an oxidizing agent having a property of increasing the heattransferable property thereof and a binder on a base support sheet isbrought into contact with a material to be transfer printed, saidcontact being made with the pattern-formed surface of the heat transferprinting sheet, and the whole is heated under a pressure to effect thetransfer of the basic dye but not of the oxidizing agent and the binderand thereafter the heat transfer printing sheet is peeled off from thelatter to transfer print the optional pattern on the material to betransfer printed.

The present invention will now be explained in detail in the following.

As examples of the base support sheet which may be used according to thepresent invention, it is preferable to use one which is not effectedunder various conditions for forming optional patterns and also heattransfer printing and therefore there are mentioned for example variouskinds of papers and coverted papers, cellophane, film and sheets ofvarious resins having a thermal resistance, various metal foils andplates and laminated films made of them.

The basic dye which is used according to the present invention includesthe so-called basic dyes and cationic 3 dyes.

Examples of the basic dyes which are used according to the presentinvention are basic dyes and cationic dyes which have been substantiallyused in a prior sublimating transfer printing method and which have acomparatively poor heat transferability property in the heat transferprinting of these dyes onto other base material due to a phenomena suchas heat-melting, -evaporation or -sublimation.

The above mentioned dyes are for example methine (cyanine) type basicdyes or cationic dyes such as mono-methine type, di-methine type ortri-methine type dyes, for example 3,3-diethyloxacyanine iodide,Asotrazon Pink FG (Bayer, C.l.480l5), 2,2-carboxyanine (01.808), AstraPholoxine FF (CI. 48070), Astrazon Yellow 7GLL (C.I. Basic Yellow 21),Aizen Cathilon Yellow 3GLl-l (Hodogaya Chemical K.K. CI. 48055) andAizen Cathilon Red 68H) CI. 48020); diphenylmethane type basic dyes orcationic dyes such as Auramine (Cl. 655); tryphenylmethane type basicdyes or cationic dyes such as Malachite Green (C.l. 42000), BrilliantGreen (C.l. 42040), Magenta (CI. 42410), Methyl Violet (CI 42535),Crystal Violet (CI. 42444), Methyl Green (Cl. 684) and Victoria Blue B(CI. 44045); xanthene type basic dyes or cationic dyes such as pyronineG (Cl. 739), Rhodamine 13 (CI. 45170) and Rhodamine 6G (CI. 45160);acridine type basic dyes or cationic dyes such as Acridine Yellow G(C.l. 785), Rheomine AL (CI. 46075), Bensoflavine (CI. 791), andphosphine (CI. 46045); quinoneimine type basic dyes or cationic dyessuch as Neitral Red (CI. 50040), Astrazon Blue BGE/X 125% (CI. 51005)and Methylene Blue (CI. 52015; and other basic or cationic dyes such asanthraquinone type dyes having a quaterary amine.

The oxidizing agent which may be used in the heat transfer printingsheet is one having a property of increasing the heat transferabilityproperty through the reaction of the basic dye therewith.

As examples of the oxidizing agent, there are mentioned for examplepermanganic acid or its salts such as potassium and sodiumpermanganates; chromic acid or its related compounds such a potassiumchromate, potassium bichromate, sodium and ammonium chromates, sodiumand ammonium bichromate, magnesium and calcium chromate, potassiumchlorochromate and chromye chloride; peroxides such as hydrogen peroxideand sodium, barium and calcium peroxides and nitrates such as potassium,sodium and ammonium nitrates.

According to the present invention, the amount of the above oxidizingagent employed is preferably 0.1 to 20 molar equivalent of oxidizingagent per molar equivalent of the basic and more preferably is 1 tomolar equivalent per molar equivalent of the basic dye.

The heat transfer printing sheet can be produced by various methods.

For example, an ink or paint composition comprising as a main componenta binder, basic dye and oxidizing agent is applied onto any base supportsheet as an optional monoor multi-color pattern of for example a letter,mark and figure by a normal printing, drawing or painting method, andthereby a heat transfer printing sheet on which the optional pattern isformed on the base support sheet of the basic dye and oxidizing agentare present on the optional pattern part can be produced.

As an alternative procedure, an ink or paint composition comprising as amain component a binder and basic dye is firstly applied onto any basesupport sheet as an optional monoor multi-color pattern by a normalprinting, drawing or painting method and then a composition comprisingas a main component the oxidizing agent is secondly applied on the aboveoptional pattern, and a heat transfer printing sheet on which theoptional pattern is formed on the base support sheet and the basic dyeand oxidizing agent are present on the optional pattern part can beproduced.

As another alternative procedure, inversely, a composition comprising asa main component the oxidizing agent is firstly applied onto any basesupport sheet as an optional pattern by the same method as the above andthen an ink or paint composition comprising as a main component thebinder and the basic dye is secondly applied onto the optional pattern,and thereby an optional monoor multi-color pattern is formed on the basesupport sheet and the heat transfer printing sheet on which the basicdye and oxidizing agent are present on the optional pattern part can beproduced.

As a further alternative procedure, an ink and paint compositioncomprising as a main component a binder and a basic dye which ispreviously treated with a composition comprising as a main component theoxidizing agent is applied onto any base support by a normal printing,drawing or painting method to form a monoor multi-color pattern thereon,and thereby a heat transfer printing sheet on which an optional patternis formed and the above basic dye and oxidizing agent are present on theoptional pattern part.

According to the present invention it is preferable to produce a heattransfer printing sheet by selecting the most beneficial method from theabovementioned methods for the production thereof depending upon thedesired purpose.

The above mentioned processes for the production of a heat transferprinting sheet according to the present invention can be used together.

The optional pattern which may be formed on a base support sheetaccording to the present invention may be a wholly covered layercontaining the basic dye and oxidizing agent.

As examples of the binder which may be used for the process ofproduction of the above heat transfer printing sheet, there arementioned well known binders such as for example, methyl cellulose,ethyl cellulose, carboxymethyl cellulose, cellulose acetate, cellulosebutyrate and sodium alginate and its derivatives; polyvinyl alcohol;polyvinyl acetate; polycarbonate resin; polyester resin; polyamideresin; phenol resin; aminoplast resin; homopolymers or copolymers ofvarious vinyl monomers such as unsaturated carboxylic acids such asacrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleicacid or ester-, nitrileor amide derivatives of these unsaturatedcarboxylic acids, vinyl chloride, vinylidene chloride, vinyl acetate,styrene, vinylpyrrolidone, vinyl methyl ether, butadiene, ethylene andpropylene; starch; gun arabic; tragacanth gum and gelatin.

The above-mentioned binder which soften or melt at the heatingtemperature under the heat transfer printing conditions are notpreferable for the purpose of the present invention. When the binderswhich soften or melt are used, the binders themselves are also heattransfer printed on the base material to be heat transfer printed andconsequently heat transfer printed articles having a poor handlingquality are obtained.

According to the above mentioned methods for the production of a heattransfer printing sheet, if necessary in addition to the binder, basicdye and oxidizing agent, a coloring assistant having an effect that itpenetrates into the base material to be heat transfer printed at thetime of heat transfer printing to swell the intermicelles and thereby toincrease the penetration of the basic dye, or various addition agentswhich can regulate the state of the composition comprising the basicdye, binder or oxidizing agent can be used.

The coloring assistant includes for example, urea, naphthalene, ammoniumtartrate, glycine A, the oxalate of an aliphalic amine such ascyclohexylamine, ammonium acetate, benzylamine and various surfaceactive agents having an anionic, nonionic or amphoteric property.

The addition agents include for example a plasticizer, stabilizer, wax,grease, drier, auxiliary drier, hardener, emulsifier, viscosityincreasing agent, filler and dispersing agent.

In the process for the production of a heat transfer printing sheet asdescribed above, the composition comprising the basic dye, oxidizingagent and position comprising the basic dye, oxidizing agent and binderis in any state, for example solution-, emulsion-, suspensionorsol-state.

When the heat transfer printing sheets according to the presentinvention which are produced by the above-mentioned process are piled upin order to store them, there are disadvantages that the basic dyehaving a poor heat transferable property and the oxidizing agent havinga property of increasing the heat transferable property of the basic dyewhich constitute a pattern in one heat transfer printing sheet aretransferred into the base support sheet of another heat transferprinting sheet to contaminate it, and consquently the quantity of thebasic dye of the former heat transfer printing sheet is decreased. Whenit is used, therefore, the concentration of the basic dye to be heattransfer printed is gradually faded, or even if the transfer printing iseffected the color tone obtained is not clear, or in very bad cases itcannot be used.

Therefore, it cannot be said that the aforesaid heat transfer printingsheet is always completely satisfactory from the point of storage life.

According to the present invention, in such case, it is preferable touse a heat transfer printing sheet wherein a pattern comprising a basicdye having a poor heat transferable property, an oxidizing agent havinga property of increasing the heat transferable property of the basic dyeand a binder is formed on a base support sheet and then a film of resinthrough which the basic dye cannot be passed when the heat transferprinting is not carried out, but can be passed when the heat transferprinting is carried out is applied on the pattern.

When the heat transfer printing sheet as described above is used, theaforesaid disadvantages can be overcome by the application of the resinfilm and the storage life of the sheet can be very much prolonged.

As the examples of resin which can be used as a film having the propertyas described above, there are preferably mentioned for examplesodiurnpolyacrylate, polyvinyl alcohol, dextrin, methyl cellulose,carboxymethyl cellulose, polyvinyl-pyrolidone, vinylmethylether-acrylicacid copolymer, water-soluble thermosetting acrylic resin, rosinmodified maleic resin ester gum,

rosin modified phenol resin, xylene resin, polyacrylic ester, butyralresin, epoxy resin and polystyrene. These resin films may be formed by anormal coating method such as gravure-coating method, roll-coatingmethod, barcoating method, silk-screen coating method, airknife coatingmethod, spray coating method and the like. The quantity of resin to bepainted is preferably 0.2 4.0 g/m depending upon the kind of resin.

Among these resins, it is preferable to use water-soluble resins such aspolyvinyl alcohol, sodium polyacrylate and polyvinyl pyrrolidone andoil-soluble resins such as xylene resin, rosin modified phenol resin,polyvinyl butyral, epoxy resin, polystyrene and petroleum resin, becausethese resins not only to not contaminate the base support sheet but alsodo not damage the heat transfer printing property of the basic dye andthus the heat transfer printing having an accurate pattern can beobtained.

The production of the above heat transfer printing sheet is carried outby forming any monoor multicolor pattern such as for example a letter,mark and figure on the base support sheet by a normal printing, drawingor painting method using an ink or paint composition containing as amain component the basic dye, oxidizing agent and binder, and therebythere are obtained a sheet in which the basic dye and oxidizing agentare present in any part of the pattern.

As an alternative process of the present invention, any monoormulti-color pattern is formed on any base support sheet by a normalprinting, drawing or painting method using an ink or paint compositioncontaining as a main component the basic dye and binder and then byapplying a composition containing as a component the oxidizing agentonto the above pattern, there is obtained a sheet in which the basic dyeand oxidizing agent are presented in any part of the pattern.Conversely, any monoor multi-color pattern is formed on any base supportsheet by the same method as described above using a compositioncontaining as a main component the oxidizing agent and then by applyingan ink or paint composition containing as a main component the basic dyeand the binder, there is obtained a sheet in which the basic dye and theoxidizing agent are presented in any part of the pattern.

As a further alternative process of the present invention, the basic dyeis previously treated with a composition containing the oxidizing agentas a main component and then any monoor multi-color pattern is formed onthe base support sheet by a normal printing, drawing and painting methodusing an ink or paint component containing as a main component the abovetreated basic dye and the binder, and thereby there is obtained a sheetin which the basic dye and the oxidizing agent are presented in any partof the pattern.

Furthermore, a resin composition containing as a main component a resinthrough which the basic dye can not be passed when the heat transferprinting is not carried out, but can be passed when the heat transferprinting, can be carried out is coated onto the patternformed surface ofthe above-mentioned sheet in whcih the basic dye and the oxidizing agentare presented in any part of the pattern, for example by coating methodssuch as roll coat, gravure coat, bar coat, air knife coat and screencoat. As other methods therefore, the heat transfer printing sheet ofthe present invention can be obtained by laminating a film or sheet, ofresin through which the basic dye can not be passed when the heattransfer printing is not carried out, but can be passed 7 when the heattransfer printing is carried out, on the pattern-formed surface of theabove-mentioned sheet in which the basic dye and the oxidizing agent arepresented in any part of the pattern.

According to the heat transfer printing sheet of the present invention,on the other hand, the basic dye passes through optionally the basesupport sheet depending upon the kind of the material thereof. In thiscase, the base support sheet can be previously formed with a film ofresin through which the basic dye and the oxidizing agent are not passedthrough under nonheateing conditions.

Namely, the heat transfer printing sheet of the present invention may bethe sheet in which the base support is applied with a resin film throughwhich the basic dye having a poor heat transferable property and alsothe oxidizing agent having a property of increasing the heattransferable property of the basic dye are not passed and then a patterncomprising the basic dye and the oxidizing agent can be formed onto theresin film, and further a resin film throught which the basic dye cannot be passed during the non-heat transfer printing but can be passedduring the heat transfer printing can be covered on the pattern.

As an examples of the resin which does not pass the basic dye and theoxidizing agent through the base support and may be used in the heattransfer printing sheet of the present invention, there are mentionedpolyvinyl alcohol, sodium polyacrylate, polyacrylamide, dextrin, methylcellulose carboxymethyl cellulose, polyvinylpyrrolidone,vinylmethyletheracrylic acid copolymer, water soluble thermosettingacrylic resin, British gum, casein, Crystal gum, gum arabic, tragacanthgum, ester gum, rosin modified phenol resin, hard resins such as xyleneresin, acrylic esters, butyrak resin, epoxy resin, aceto-butyriccellulose and thermal setting acrylic resin. Among these, it isespecially preferable to use water soluble resins such as sodiumpolyacrylate, polyvinyl alcohol, dextrine and polyvinyl pyrrolidone andoil soluble resins such as rosin modified phenol resin, xylene resin,polyvinyl butyral, epoxy resin, polystyrene and petroleum resin.Although the coating amount of the resin is different depending upon thekind of resin, it is preferably 0.2 to 4 g/m and the coating can beeffected by various coating machines such as a gravure coating machine,silk screen or airknife.

The production of the above heat transfer printing sheet may be carriedout for example by coating the composition containing as a maincomponent the resin on the base support sheet with the same coating asdescribed above, or by laminating the film or sheet of the resin whichis manufactured by a normal method on the base support sheet to form anundercoat layer on the latter and then by applying the before-mentionedheat transfer printing sheet in the manner described above on theundercoat formed on the base support sheet.

In the case of using as the base support sheet, for example, aluminumfoil, a film or sheet of resin, rubber sheet, glassine paper having veryhigh density and parchment paper, it is not necessary to apply on thebase support sheet a film through which the basic and the oxidizingagent can not be passed when the heat transfer printing is not effected.

In the present invention, it is preferable to produce the heat transferprinting sheet by selecting a very economical method fromthe'above-mentioned methods depending upon the desired object.

In the present invention, furthermore, two or more coats or laminates ofthe resin through which the basic dye and the oxidizing agent can not bepassed when the heat transfer printing is not effected and also throughwhich the basic dye and the oxidizing agent can not be passed when theheat transfer printing is not effected but can be passed when the heattransfer printing is effected may be used.

In connection with the coating of the resin, it is necessary that thepattern provided on the base support sheet not be effected, for exampleit is necessary that the letter, mark and figure provided on the basesupport sheet is not damaged.

The process for heat transfer printing according to the presentinvention is specifically explained in the following:

Firstly, the surface of the pattern or resin film of the heat transferprinting sheet is laminated so as to contact with the surface of thematerial to be transfer printed and the whole is heated under pressurebetween two heated pressing plates or is heated and pressed by passingthough two heated rollers to effect the transfer of the basic dye butnot of the oxidizing agent and the binder and then heat transferprinting sheet is peeled off from the material which was heat transferprinted.

By this process, it is possible to manufacture the heat transfer printedproduct in which only the basic dye in any pattern of heat transferprinting sheet is transferred onto the material to be transfer printedand which has very clear color tone and various fastness properties.

In the above heat transfer printing process, it be not necessary thatthe heating temperature is higher than the melting point or sublimatingpoint of the basic dye itself which is used for the production of theheat transfer printing sheet, and although the heating temperature isvaried depending upon the kind of the basic dye it is preferable tooptionally use a temperature in the range of about to 250C.

The condition of the pressure is preferably about 50 g/cm to 20 kg/cmThe duration of heating and pressing treatment is preferably about 30 toseconds.

In the present invention, furthermore, it is possible to carry out theheat transfer printing process by using the heat transfer printing sheetformed with the color layer containing the basic dye, oxidizing agentand binder which covers the whole surface thereof, and a masking memberhaving an optional open pattern is laminated on the color layer of theheat transfer printing sheet, and then a material to be transfer printedis laminated on the masking member and the whole is heated underpressure.

As examples of the masking member, there are mentioned stencil papersfor mimeographing such as stencil paper for hand writing, typewritingand ball pen writing, and heat sensitive stencil paper which have formedthereon an optional open pattern such as a letter, mark or figure; ascreen printing plate (stencil for screen printing) having an optionalpattern for use in screen printing; and films and sheets of varioussynthetic resins, various papers and various metal foils and thin metalsheets which are formed with an optional open pattern such as a letter,mark, figure or design by a punching or corroding treatment.

In addition to the above masking member, it is possible to usephotosensitive dry films such as Liston film (Du pont) and Raminerfilm(Dynachem) which are 9 formed with an optional open pattern by normalexposing, developing and fixing.

The material to be transfer printed which may be used in the process forthe heat transfer printing process according to the present inventionincludes vegetable fibers such as cotton and hemp fibers; animal fiberssuch as wool and silk fibers; glass fiber; rayon fiber, acetate andstaple fibers; various fibers such as polyamide, polyester,polyacrylonitrile, polypropylene, polyvinyl chloride, and polyvinylalcohol fibers; films and sheets of various synthetic resins; variouspape'"; foils and plates of various metals; glass plate; potteries;leather, collagen and synthetic leather; rubber sheet and mould; wood;plywood; slate plate; hard board; gypsum board; and complex materialsmade of organic compounds and inorganic compounds.

The process for heat transfer printing process can be simply carried outby the use of a heating iron at the time of heating under pressure andconsequently this step is easy.

According to the present invention, after an optional pattern is heattransferred on the material to be transfer printed, on the base materialis subjected to a steam heating or acid-steam heating treatment toobtain a clearer coloring. It is worth noting in this case that thetreatment time, namely the time which is necessary for the completecoloring of the basic dye is very much shorter than that of the priorprinting method using a coloring ink containing vehicle.

As is clear from the above explanation, according to the presentinvention, the heat transfer printing is carried out using a heattransfer printing sheet in which an optional pattern comprising a basicdye having a poor heat transferable property based upon heat-melting,-evaporation or -sublimation phenomena and an oxidizing agent having theproperty of increasing the heat transferable property through the actionof a basic dye with the oxidizing agent and a binder is formed on a basesupport sheet.

By such fact, therefore, there are very valuable advantages that thebasic dye which was scarcely used in the prior sublimation transferprinting process due to the fact that the phenomena such asheat-melting, -evaporation or -sublimation is comparatively poor can beapplied for the sublimation transfer printing process. As a result, theapplication range of the material to be transfer printed can be verymuch enlarged by the fact that the basic dye can be used in the presentinvention. Since only disperse dyes could be used in the priorsublimation transfer printing process, the fiber as the material to betransfer printed was limited to polyester type fiber. In the process ofthe present invention, on the other hand, by suitably selecting thebasic dye any fiber which is suitable for coloring with said basic dyecan be easily colored. By using the basic dye, for example a syntheticfiber such as polyacrylonitrile fiber and animal fibers such as silk andwool can be colored.

In the process of the present invention, the heat transferable propertycan be considerably increased by reacting the basic dye which wasscarcely used in the prior sublimation transfer printing process due tothe fact that the phenomena such as heat-melting, -evaporation or-sublimation is poor by the use of the oxidizing agent, and also whenthe oxidizing agent-treated basic dye is once heat transfer printed onthe material to be transfer printed, it is returned to the originalbasic dye. Therefore, the fixed color has various considerable superiorfastness such as weather resistance, abra- 10 sion resistance, heatresistance, solvent resistance, water resistance and chemicalresistance. By applying furthermore a stream heating treatment, a heattransfer printed article having more clear color tones can be obtained.

By using the heat transfer printing sheet of the present invention, thestorage life and easy handling are improved and the contamination isdecreased. Therefore there is the advantage that the value of thecommodity can be highly increased.

In order that the present invention may be well understood, thefollowing examples are given by way of illustration only. Unlessotherwise stated, quantities are expressed as parts by weight.

EXAMPLE 1 parts of polyvinylbutyral resin (Sekisui Chemical Co., Ltd.:Trade name: Eslex BL-l) were dissolved in 900 parts of a mixed solventof xylene and ethanol (7:3). 900 parts of the obtained solution wasmixed with a solution of 50 g of sodium bichromate in 50 g of water (pH3.2) and then the whole was sufficiently agitated. 900 parts of themixture and 100 parts of Aizen Cathilon Blue 5G (C.I. 51005; Color tone:Blue) were thoroughly kneaded together in a ball mill to obtain a blueink composition.

Using Aizen Cathilon Red 68H (C.I. 48020; color ton: Red) and AizenCathilon Yellow 3GLH (C.I. 48055; Color tone: Yellow), similarly, a redink composition and a yellow ink composition were respectively obtained.

Using the above obtained blue ink composition, red ink composition andyellow ink composition, a heat transfer print sheet for a multi-colorprinting was obtained by printing a desired pattern with a gravureprinting procedure onto a paper for a gravure printing. The heattransfer printing sheet was laminated with a plain weave cloth made ofpolyacrylonitrile fibers having a thickness of 0.4 mm and the whole washeated with a heated plate of l90C for 60 seconds and then a deep andclear multi-color heat transfer printed cloth was obtained by strippingoff the heat transfer printing sheet. The obtained printed cloth waslaminated with a white cloth made of acrylonitrile fibers and then thewhole was heated at C for 15 seconds. As a result, the sublimtionfastness shows Grade 4 5 and the white cloth was not contaminated. Thelight fastness of the blue, yellow and red colors showed respectivelyGrades 5, 6 and 3 so that they were good. The wash fastness, abrasionfastness and dry-cleaning fastness were respectively Grade 5. Thereforevarious fastness properties showed a good result.

The above procedure was repeated except that the following dyes wereused in the place of the above dyes. Similar results were obtained.

a. Aizen Basic Cyanine 6Gl-l (C.I. 42025; Color tone:

Turquoise) b. Aizen Methylene Blue FZ (C.l. 52015; Color tone:

Blue) c. Aizen Cathilon Brilliant Yellow SGLH (C.I. Basic Yellow 13;Color tone: Yellow) d. Astrazon Red 68 (C.I. 48020; Color tone: Red) e.Aizen Cathilon Orange RH (C.I. 48040; Color tone: Orange) f. AizenMalachite Green (C.I. 42000; Color tone:

Green) g. Aizen Cathilon Brilliant Pink BF (C.I. Basic red 36; Colortone: Pink) h. Astrazon Pink FG (CI. 48015; Color tone: Pink) i.Astrazon Blue 86 F/X 120% (CI. 51005; Color tone: Turquoise) j. Mixtureof Aizen Cathilon Blue G (C.l. 51005) and Aizen Cathilon Yellow 3GCH(CI. 48055) in the weight ratio of 1:1 [Color tone: Green] k. Mixture ofAizen Cathilon Blue 50 (C.l. 51005) and Aizen Cathilon Red 6BH (C.l.48020) in the weight ratio of 4:6 [Color tone: Violet] Mixture of AizenCathilon Red 68H (CI. 48020) and Aizen Cathilon Yellow 3GCH (C.l. 48055)in the weight ratio of 2:8 [Color tone: Orange] When the above basicdyes are used without the oxidizing agent the heat transfer printingproperty is inferior to the case of using the oxidizing agent.

EXAMPLE 2 90 parts of ethyl cellulose (Hercules: Trade name Ethylcellulose N7CP), 90 parts of Aizen Cathilon Red 6811 (CI. 48020) and 90parts of potasium bichromate were added into 770 parts of a mixedsolvent of xylene and ethanol (8:2) and the whole was sufficientlykneaded in a ball mill to obtain a red ink composition. Using theobtained red ink composition, a heat transfer printing sheet wasobtained by printing a desired pattern with a gravure printing procedureonto a paper from a gravure printing. This heat transfer printing sheethas similar properties as described in Example 1.

When this example was repeated except that potassium permaganate wasused in the place of potassium bichromate, similar result was obtained.

EXAMPLE 3 950 parts of aqueous solution of polyvinyl alcohol (NipponSynthetic Chemical Industry Co., Ltd.; Trade name: Gohsenol GSS1173)were sufficiently kneaded together with 50 parts of ammonium bichromate.900 parts of the obtained aqueous solution of ammonium bichromate and100 parts of Aizen Cathilon Blue 50 (CI. 51005) were sufficientlykneaded in a ball mill to obtain a blue ink composition.

Using the obtained blue ink composition, a heat transfer printing sheetwas obtained by printing a desired pattern with a silk screen procedureonto a paper for a gravure printing. The heat transfer printing wascarried out by using the above heat transfer printing sheet as describedin Example 1. A sufficient heat transfer printing property was obtained.

EXAMPLE 4 100 parts of ethyl cellulose N7CP and 100 parts of AstrazonBlue BG E/X were mixed together with 800 parts of a solvent mixture ofxylene-butanol (8:2) in a ball mill and then the whole was sufficientlykneaded to obtain a blue ink composition.

Using the obtained blue ink composition, a desired pattern was printedonto a paper for a gravure printing by a gravure printing procedure. 6parts of potassium bichromate were dissolved in 94 parts of 4% aqueoussolution of methyl cellulose (Shinetsu Chemical Co., Ltd.; Trade name:Metolose 6581-150). The obtained solution was over-coated on the dyelayer of the printed paper by the use of Mayerbar No. 4 and then theovercoat was sufficiently dried to obtain a heat transfer printingsheet. The heat transfer printing sheet was laminated with a plain weavecloth made of polyacrylonitrile fibers having a thickness of 0.4 mm andthe whole was pressed with press plates heated at 190C for 12 60seconds, and thereby a deep blue heat transfer printed cloth wasobtained.

EXAMPLE 5 100 parts of sodium bichromate were dissolved in 900 parts of15% aqueous solution of polyvinyl alcohol (Nippon synthetic ChemicalIndustry Co., Ltd; Trade name: Gohsenol 6581173). 55 kg/m of U-lap(Kasuga paper making Co., Ltd.) were coated with the above solution by agravure printing machine. The coating quantity was 3 g/m The abovesurface of the coating was printed with a desired pattern of a blue inkcomposition used in Example 4 to obtain a heat transfer printing sheet.By using this heat transfer printing sheet, a heat transfer printing wascarried out in a similar manner as described in Example 4. Similar heattransfer printing effect was obtained.

EXAMPLE 6 100 parts of ethyl cellulose N7CP, 100 parts of Aizen CathilonRed 68H, 20 parts of sodium bichromate and 20 parts of water werecharged into a ball mill together with 760 parts of the mixture ofxylene-butanol (8:2) and then the whole was sufficiently kneaded toobtain a red ink composition. By using the above red ink composition, adesired pattern was printed on a paper for a gravure printing by agravure printing procedure. Then 6 parts of urea (Jynsei Chemical Co.,Ltd.) were added with 94 parts of 15% aqueous solution of polyvinylalcohol GL-OS to uniformly dissolve the former into the latter. Theaqueous polyvinyl alcohol in which urea is dissolved was over-coated onthe dye layer of the printed pattern by using Mayerbar No. 4 to obtain aheat transfer printing sheet.

The heat transfer printing sheet was laminated with a cloth made ofpolyacrylonitrile fibers and the laminated material was heated at 190Cwith an iron for 45 seconds. The obtained heat transfer printed clothshows very good dyability and was colored with a clear deep red. Theurea showed that the permeability of the dye into the cloth and thecolor developing property are considerably increased.

EXAMPLE 7 Using the following kinds of oxidizing agents as the oxidizingagent which should be acted with a basic dye or cationic dye, an inkcomposition was prepared in a ball mill. The ink composition was printedon the base support sheet to obtain a heat transfer printing sheet. Theheat transfer printing property of the obtained sheet was very good andcould be increased.

1. Chromic anhydride 10 parts of chromic anhydride were dissolved inparts of 4% aqueous solution of methyl cellulose (Shinetsu Chemical Co.,Ltd.; Trade name: Metolose 65 SHSO), 10 parts of Aizen cathilon Red 6BHwas added to 90 parts of the above solution and then sufficientlykneaded in a ball mill to obtain a red ink composition. A heat transferprinting sheet was produced by the use of the red ink composition.

2. Potassium nitrate The following ink composition was sufficientlykneaded in a ball mill to obtain a green ink composition. Using thegreen ink composition a heat transfer printing sheet was produced.

Ethyl cellulose parts l4partsr Similar result was obtained by usingsodium nitrate in the place of potassium nitrate.

3. Hydrogen peroxide solution A yellow ink composition was prepared from100 parts of ethyl cellulose N7CP, 100 parts of Aizen Cathilon Yellow3GLH and 800 parts ofa solvent mixture of xylene and butanol (8:2). Apaper for gravure printing was printed with the yellow ink composition.Then the coating solution prepared by dissolving 4 parts of hydrogenperoxide solution into 96 parts of 40% aqueous solution of Metolose wascoated on the above printed surface by Mayerbar No. 4 to obtain a heattransfer printing sheet.

4. Potassium chromate 800 parts of 12% solution of ethyl cellulose inxyleneethanol mixture (7:3), 100 parts of Malachite green and 100 partsof a saturated aqueous solution of potassium chromate (25C) weresufficiently kneaded in a ball mill to obtain a green ink composition. Aheat transfer printing sheet was obtained by the carrying out ofdefinite printing.

Similar result was obtained when ammonium chromate was used in the placeof potassium chromate.

5. Sodium permanganate 100 parts of sodium permanganate was dissolved in90 parts of 4% aqueous solution of Metolose 100 parts of Aizen CathilonBlue G were added to the above solution containing the oxidizing agentand then the whole was sufficiently kneaded to obtain a blue inkcomposition. A heat transfer printing sheet was obtained by printing theblue ink composition on a paper for a gravure printing.

6. Anhydrous barium peroxide 100 parts of anhydrous barium peroxide wereadded to 900 parts of 4% aqueous solution of Metolose and thensufficiently kneaded. 100 parts of Aizen Cathilon Red 6BH were added to900 parts of the above barium peroxide dispersion and then sufficientlykneaded in a ball mill to obtain a red ink composition. A heat transferprinting sheet was obtained by printing the red ink composition on apaper for a gravure printing.

7. Magnesium chromate 100 parts of magnesium chromate were dissolved in900 parts of 4% aqueous solution of Metolose and then 100 parts ofMalachite green were added to 900 parts of this solution and thensufficiently kneaded in a ball mill to obtain a green ink composition. Aheat transfer printing sheet was obtained by printing the green inkcomposition on a paper for a gravure printing.

8. Mixture of anhydrous barium peroxide and sodium bichromate 50 partsof anhydrous barium peroxide and 50 parts of sodium bichromate wereadded to 900 parts of 4% aqueous solution of Metolose and then the wholewas sufficiently kneaded. The 100 parts of Aizen Cathilon Red 6BH wereadded to 900-parts of the above barium peroxide dispersion and thensufficiently kneaded in a ball mill to obtain a red ink composition. Aheat trans fer printing sheet was obtainedby printing the red inkcomposition on apaper for a gravure printing.

14 9. Mixture of sodium permanganate and magnesium chromate 50 parts ofsodium permanganate and 50 parts of magnesium chromate were dissolved in900 parts of 4% aqueous solution of Metolose. parts of Aizen CathilonBlue 5G were added to 900 parts of this aqueous solution of theoxidizing agent and then sufficiently kneaded in a ball mill to obtain ablue ink composition. A heat transfer printing sheet was obtained byprinting the blue ink composition on a paper for a gravure printing.

EXAMPLE 8 80 parts of Crystal Violet (CI. 42555) were dissolved in l720parts of water and then 200 parts of 20% aqueous solution of sodiumdichromate were gradually added to the above dye solution and finallyafter the completion of the addition the solution was left to stand. Theformed precipitate was filtered off from the solution and washed anddried. Then 70 parts of Crys tal Violet treated with the above oxidizingagent and parts of ethyl cellulose N7CP were mixed with 810 parts ofmixed solvent of xylene and butanol (8:2) and the whole was sufficientlykneaded in a ball mill to obtain a violet ink composition. Using theviolet ink composition, the desired pattern was printed on a paper for agravure printing by a gravure printing procedure to give a heat transferprinting sheet. The heat transfer printing sheet was laminated with aplain weave cloth made of polyacrylonitrile fibers and the whole washeated with heated plates at C for 60 seconds. As a result, a deepviolet-color heat transfer printed cloth was obtained.

EXAMPLE 9 SP base paper 64 g/m (Honshu Paper Making Co., Ltd.) wasprinted with the desired pattern in a gravure printing machine using theyellow, red and blue inks having the following respective composition toobtain a multi-color printed material.

The printing speed was 30 m/min.

Then the multi-colorprinted material was coated by using 15% aqueoussolution of polyvinyl alcohol (Nippon Synthetic Chemical Industry Co.,Ltd.: Trade name: Gohsenol G88 1 173) in a gravure rotary printingmachine to obtain a heat transfer printing sheet. The coating speed was20 m/min. The drying was also com- 15 pletely carried out. The coatingquantities was about 1.2 g/m The contamination of the heat transferprinting sheet having an overcoat resulting from time lapse was comparedwith that of the heat transfer printing sheet having no overcoat. Thesheet of the present invention shows a storage life of about 3 monthsand about 3 to 4 times the storage life in comparison with the sheethaving no overcoat. Similar result was obtained in the heat transferprinting sheets which were applied with an overcoat having respectivelythe coating quantities of about 2 g/m and consisting of two layers ofsodium polyacrylate, polyvinyl pyrrolidone or polyvinyl alcohol andbutyral resin or polystyrene in the place of polyvinyl alcohol onlywhich is a watersoluble resin. The heat transfer printing method usingthe heat transfer printing sheet which is prepared as above was carriedout as follows:

The above heat transfer printing sheet was laminated with a plain weavecloth made of polyacrylonitrile fibers having a thickness of 0.4 mm andthen the whole was heated by a heated plate at 190C for 75 seconds andSP base paper of the above heat transfer printing sheet was stripped andthereby clear yellow-, redand blue-color heat transfer printed clothswere obtained. The obtained printed cloths show a good fastness, namelywashing fastness grade 5, abrasion fastness grade 5, drycleaningfastness grade 5 in Japanese 1ndustrial Standard and sublimationfastness shows grades 4 to 5 at 180C, for 15 seconds.

EXAMPLE Example 9 was repeated except that in the place of thewater-soluble resin which was used for the overcoat butyral resin(Sekisui Chemical Co., Ltd.; Trade name: Eslex BL-l was used and wasdissolved in a mixed solvent of toluene-alcohol to prepare solution andthe coating quantities were about 2.0 g/m The obtained heat transferprinting sheet shows a good result similar to Example 9 in the point ofthe storage life and heat transferring property due to the time lapse.

When oil-soluble resins such as polystyrene, epoxy resin, petroleumresin and xylene resin were used in the place of butyral resin in theabove example, similar result was obtained.

EXAMPLE 12 The under-mentioned painting liquid was undercoated on U-lap(Kasuga Paper Manufacturing Co., Ltd: 55kg/m in a rotary gravureprinting machine. The drying was sufficiently carried out. The paintingquantities were 2 to 3 g/m Then the paper with the undercoat was printedwith the ink composition as used in Example 9 by the same procedure ofExample 9 in a gravure printing machine to obtain a multi-color printedmaterial. The under-mentioned coating liquid was coated on the printedsurface of the above multicolor printed material to obtain a heattransfer printing sheet with an over-coating layer. The coating methodis carried out as in Example 9. The painting quantities of the coatingwere was about 1 to 2 g/m.

The storage life of the heat transfer printing sheet having undercoatand overcoat was compared with that of the heat transfer printing sheethaving no undercoat and overcoat.

The process for the testing of contamination of these transfer printingsheets was as follows:

The ink-printed surface of the transfer printing sheet was laminatedwith one white paper (white paper 1) and also the non-printed surface ofthe transfer printing sheet was laminated with one white paper (whitepaper 2) and then the whole was charged in a blocking tester to storageat 30C for three months therein, thereby the contamination of thetransfer printing sheet was determined by the contamination degree ofwhite papers 1 and 2.

1n the transfer printing sheet having no undercoat and overcoat, whitepapers 1 and 2 were extremely contaminated. 1n the transfer printingsheet having undercoat and overcoat which are applied thereon by usingthe under-mentioned resins, on the other hand, a good storage life wasattained and the contamination of white papers 1 and 2 could not behardly found.

The heat stability of the transfer printing sheet having undercoat andovercoat was good as similar as in Example 9 and a clear colored clothwas obtained.

The compositions of coating liquids for the undercoat and overcoat areshown in Table 1.

Table 1 Nos. Undercoating liquid Overcoating liquid 1 15% aqueoussolution of polyvinyl alcohol 2 15% aqueous solution of polyvinylalcohol 15% aqueous solution of polyvinyl alcohol 15% solution ofbutyral resin in toluene-isopropyl alcohol mixture (7:3) 15% aqueoussolution of polyvinyl alcohol 15% solution of butyral resin intoluene-isopropyl alcohol mixture (713) The following resins were usedin the place of the resins used for the undercoating liquid as describedin Table l. Respectively similar result as the above was obtained.

In Nos. 1 and 2 in Table 1, sodium polyacrylate, dextrine orpolyvinylpyrrolidone was used.

In Nos. 3 and 4 in Table 1, rosin modified phenol resin, xylene resin,polystyrene, epoxy resin or petroleum resin was used.

The following resins were used in the place of the resins used for theovercoating liquid as described in Table 1. Respectively, similar resultas the above was obtained.

in Nos. 1 and 2 in Table 1, sodium polyacrylate, polyvinyl pyrrolidone,two coats of polyvinyl alcohol and butyral resin or polystyrene wasused.

In Nos. 3 and 4 in Table 1, xylene resin, rosin modified phenol resin,polystyrene, epoxy resin or petroleum resin was used.

EXAMPLE 12 When the overcoating liquid was coated in Examples 10 and 11,the dye on the heat transfer printing sheet was dissolved into thesolvent of the above liquid depending upon the kinds of dyes and becauseof this the sheet was often liable to be contaminated. In such case, afirst overcoat was preliminarily applied using 15% aqueous solution ofpolyvinyl alcohol (coating quantity: 0.5 to 1.0 g/m and then wassufficiently dried and thereafter a second overcoat was finally appliedusing 15% solution of polystyrene in a mixed solvent of gaso- 1'7 linefor rubber, ligroin and toluene (3:324). Bysuchtwo coats thecontamination at the coating could be prevented.

The storage life and heat transfer printing property of the heattransfer printing sheet which was obtained in this way were good.

EXAMPLE 13 An undercoat was provided on U-lap (Kasuga PaperManufacturing Co., Ltd.:, 55 kg/m using aqueous solution of polyvinylalcohol. After the undercoat was sufficiently dried an oxidizing agentlayer was coated thereon using an oxidizing agent solution in which 60parts of Na Cr O, were dissolved in 6% aqueous solution of methylcellulose 65SH50 and then sufficiently dried. A red ink was obtained byadding 120 parts of ethylcellulose N7CP and 100 parts of Aizen CathilonRed 6Bl-l (CI. 48020) into 780 parts ofa mixed solvent of xylene andbutanol (8:2) and by sufficiently kneading the whole in a ball mill. Theabove oxidizing agent layer was printed with the red ink in a gravureprinting machine to form a desired pattern.

Thereafter, an overcoat was formed onto the pattern by using 15%solution of butyral resin in a mixed solvent of toluene and isopropylalcohol (7:3) in a gravure printing machine to obtain a heat transferprinting sheet. The coating quantity was about 1.2 g/m The storage lifeof the above sheet is good and the transfer printing property is goodwhen the transfer printing was carried out as described in Example 9.

A heat transfer printing sheet having a similar storage life asdescribed above and superior transfer printing property was obtainedwhen sodium acrylate, dextrine, epoxy resin or xylene resin was used inthe place of polyvinyl alcohol as the resin of the undercoat and alsotwo coats consisting of polystyrene or polyvinyl alcohol and butyralresin or polystyrene were used in the place of butyral resin as theresin of the overcoat.

EXAMPLE 14 Example 13 was repeated except that the ink pattern layer wasfirstly printed and then the oxidizing agent layer was secondly coated.Similar results as described in Example 13 were obtained.

EXAMPLE 15 80 parts of Crystal Violet (CI. 42555) were dissolved in 1720parts of water and then 200 parts of Na Cr O aqueous solution weregradually added thereto and after the completion of the addition thesolution was left to stand. The formed precipitate was filtered off,washed with water and then sufficiently dried. 70 parts of CrystalViolet treated with the above oxidizing agent and 120 parts of ethylcellulose N7CP were mixed and the whole was sufficiently kneaded in aball mill to obtain a violet ink composition.

An undercoat was provided on U-lap (Kasuga Paper Manufacturing Co.,Ltd.: 55 kg/m using 15% aqueous solution of polyvinyl alcohol. After theundercoat was sufficiently dried the above violet ink composition wasprinted on the above undercoat to obtain a printed matter formed withthe desired pattern. The obtained printed matter was provided with anovercoat thereon by using 15% aqueous solution of polyvinyl alcohol toobtain a heat transfer printing sheet. The coating quantity was about1.2 g/m The storage life and heat transfer printing property of theobtained transfer printing sheet was good.

A heat transfer printing sheet having a similar storage life asdescribed above and superior transfer printing property was obtainedwhen sodium acrylate, dextrined, epoxy resin or xylene resin was used inthe place of polyvinyl alcohol as the resin of the undercoat and alsotwo coats consisting of polystyrene of polyvinyl alcohol and butyralresin or polystyrene were used in the place of polyvinyl alcohol as theresin of the overcoat.

EXAMPLE 16 50 parts of Na Cr O-, were dissolved in 950 parts of 4%aqueous solution of methyl cellulose (Shinetsu Chemical Co., Ltd.; Tradename: Metolose 65SH50) and this aqueous solution containing an oxidizingagent was coated on SP base paper 64 g/m in a gravure printing machineand then the coat was sufficiently dried.

parts of ethyl cellulose N7CP and 100 parts of Aizen Cathilon Red 6BHwere mixed together with 800 parts of a mixed solvent of xylene andbutanol (8:2) and the whole was sufficiently kneaded to obtain a redink. The desired pattern was printed in a gravure printing machine onthe sheet coated with the oxidizing agent using the above red ink.

And then an overcoat was applied on the above printed surface of thesheet in a gravure printing machine using 15% aqueous solution ofpolyvinyl alcohol and the overcoat was sufficiently dried to obtain aheat transfer printing sheet.

Similar heat transfer printing sheet was also obtained when polyvinylbutyral, polystyrene or two coats consisting of polyvinyl alcohol andbutyral resin or polystyrene were used.

EXAMPLE 1? Example 16 was repeated except that the coat of oxidizingagent was applied on the printed pattern and then the overcoat wasapplied on the coat of oxidizing agent. Similar result was obtained.

EXAMPLE 18 80 parts of Crystal Violet (CI. 42555) were dissolved in 1720parts of water and 200 parts of 20% aqueous solution of Na Cr O weregradually added to the dye solution. After the completion of theaddition the whole was left to stand. The formed precipitate wasfiltered off, washed with water and sufficiently dried. Then 70 parts ofCrystal Violet treated with the above oxidizing agent and parts of ethylcellulose N7CP were mixed with 810 parts ofa mixed solvent of xylene andbutanol (8:2) and the whole was sufficiently kneaded in a ball mill toobtain a violet ink composition.

The desired pattern was printed on an SP base paper 64 g/m in a gravureprinting machine using the above violet ink composition. Then anovercoat was applied on the printed pattern in a gravure printingmachine using 15% aqueous solution of polyvinyl alcohol to obtain a heattransfer printing sheet.

EXAMPLE 19 Example 9 was repeated except that a laminate of aluminumfoils was used in the place of SP base paper 64 g/m as the base supportsheet. Similar heat transfer printing sheet was obtained.

EXAMPLE 20 The heat transfer printing propery of the basic dye treatedwith the oxidizing agent was tested in compari- 19 son with that of thebasic dye only.

The preparation of the heat transfer printing sheet using the basic dyetreated with the oxidizing agent is carried out as in Example 1, 2, 3 or7 and the heat transfer printing sheet using the basic dye only isprepared by removing the oxidizing agent from the composition ofExamples 1, 2, 3 or 7.

These heat transfer printing sheets using the basic dye treated with theoxidizing agent and using the basic dye alone were respectivelylaminated with polyacrylonitrile fiber and the whole was heated with aheated plate at 190C for 75 seconds.

The color which was obtained by using the basic dye treated with theoxidizing agent was considerably deeper, clearer and more uniform thanthat which was obtained by using the basic dye only. These results areshown as follows:

(l) Aizen Cathilon Blue 50 (0.1. 51005) Oxidizing PreparationConcentration State of agent of sheet of color colored cloth SodiumExample 7(5) 1.30 Good permanganate Anhydrous 7(6) 1.32 Good bariumperoxide Sodium 3 1.26 Good bichromate None 040 Bad, uneven (2) AizenCathilon Red 68H (C.l. 48020) The measurement of concentration of colorwas carried out with a Quantalog Refrection Densitometer Type RD-l(Macbeth Corporation).

One part of the heat transfer printing sheet using the basic dye (AizenCathilon Blue 56) only was taken, the part was laminated withpolyacrylonitrile fibers and the whole was heated with a heated plate at210C for 75 seconds. The transfer printed cloth was inferior to thetransfer printed cloth which was obtained by using the basic dye treatedwith the oxidizing agent and by heating at 190C. Namely the colorconcnetration of the former was lower than the of the latter and theuneven coloring could not be improved even if the heating temperaturewas increased. The color of the cloth was changed to yellow and it wasnot a preferable state.

EXAMPLE 21 Using the heat transfer printing sheet which was produced bythe process as described in Example 1, the heat transfer printing wascarried out by a heated iron on a cloth made of polyamide fibers(Nylon), silk or wool in the place of a cloth made of polyacrylonitrilefibers. In these cases, a good colored cloth was obtained and the resultis shown in Table 2.

The heat transfer printing cloths as described in Examples 1 to 8 weresteam-treated to complete the color fixing sufficiently and they becomemore clear.

The results are shown in Table 3.

Table 3 Steam-heating Kind of cloth Dye condition PolyacrylonitrileAizen Cathilon C 5 minutes Blue 56 Polyamide Aizen Cathilon 1 10C 3minutes Silk Aizen Cathilon 1 10C 10 minutes Red 6 BH Wool AizenCathilon 1 10C 15 minutes Blue 50 What we claim is:

l. A heat transfer printing sheet comprising a base support sheet havingformed thereon a pattern comprising a basic dye having a poor heattransferable property, and oxidizing agent which is capable ofsufficiently increasing the heat transferable property of the basic dyewhen subjected to heating during contact with a material to which thepattern is to be transferprinted so that only the basic dye can betransferred to said material, and a binder.

2. The heat transfer printing sheet of claim 1, wherein the patterncomprises an underlayer comprising the basic dye and the binder and anoverlayer comprising the oxidizing agent and the binder.

3. The heat transfer printing sheet of claim 1, wherein the patterncomprises an underlayer comprising the oxidizing agent and the binderand an overlayer comprising the basic dye and the binder.

4. The heat transfer printing sheet of claim 1, wherein the base supportsheet comprises a material selected from the group consisting of paper,converted paper, cellophane, synthetic resin films, metal foils andplates and. laminates thereof.

5. The heat transfer printing sheet of claim I, wherein the base supportsheet is made of a material having a thermal resistance property.

6. The heat transfer printing sheet of claim 1, wherein the basic dye isselected from the group consisting of methine (cyanine) basic dyes andcationic dyes, diphenylmethane basic dyes and cationic dyes,triphenylmethane basic dyes and cationic dyes, xanthene basic dyes andcationic dyes, acridine basic dyes and cationic dyes, quinoneimine basicdyes and cationic dyes, anthraquinone basic dyes and cationic dyescontaining a quarternary amine.

7. The heat transfer printing sheet of claim 6, wherein the basic dye isselected from the group consisting of Aizen Cathilon Yellow 3GLH (CI.48055), Aizen Cathilon Red 6BH (CI. 48020), Malachite Green (CI. 42000),Crystal Violet (CI. 42555), Aizen Cathilon Blue G (CI. 51005), AizenBasic Cyanine 66H (C.l. 42025), Aizen Methylene Blue FZ (C.I. 52015),Aizen Cathilon Brilliant Yellow SGLH (C.l. Basic yellow 13), AizenCathilon Orange RH (CI. 48040) and Astrazon Pink P6 (CI. 48015).

8. The heat transfer printing sheet of claim 1, wherein the oxidizingagent is selected from the group consisting of permanganic acid andpermanganate salts thereof; chromic acid and chromate, dichromate andchloride salts thereof; hydrogen peroxide; and alkali metal and alkalineearth metal peroxides.

9. The heat transfer printing sheet of claim 8, wherein said ozidizingagent is selected from the group consisting of permanganic acid,potassium permanganate, sodium permanganate, chromic acid, potassiumchromate, potassium dichromate, sodium chromate, ammonium chromate,sodium dichromate, ammonium dichromate, magnesium chromate, calciumchromate, potassium chromate, chromyl chloride, hydrogen peroxide andsodium, barium and calcium peroxides.

10. The heat transfer printing sheet of claim 1, wherein the binder isselected from the group consisting of methylcellulose, ethylcellulose,carboxymethylcellulose, cellulose acetate, cellulose butyrate, sodiumalginate, polyvinyl alcohol, polyvinyl butyral acrylate resins,polyvinyl pyrrolidone, polyvinyl methyl ether, starch, gum arabic, gumtragacanth and gelatin.

11. The heat transfer printing sheet of claim 1, wherein a resin filmthrough which the basic dye cannot be passed unless it is subjected to aheat transfer printing step but through which it can be passed when 22the heat transfer printing step is carried out is disposed on saidpattern.

12. The heat transfer printing sheet of claim 11, wherein said resin iswater-soluble and is selected from the group consisting of polyvinylalcohol, sodium polyacrylate and polyvinyl pyrrolidone.

13. The heat transfer printing sheet of claim 11, wherein said resin isoil-soluble and is selected from the group consisting of xylene resins,rosin-modified phenol resins, polyvinyl butyral epoxy resins,polystyrene and petroleum resins.

14. The heat transfer printing sheet of claim 11, wherein said resinfilm is a laminated film consisting of at least two different resinfilms.

15. The heat transfer printing sheet of claim 1, wherein the basesupport sheet is preliminarily coated with a resin film through whichthe basic dye cannot be passed unless it is subjected to a heat transferprinting step.

16. The heat transfer printing sheet of claim 1, wherein the basesupport sheet is preliminarily coated with a resin film through whichthe basic dye cannot be passed unless it is subjected to a heat transferprinting step and also wherein the pattern is coated with a resin filmthrough which the basic dye cannot be passed unless it is subjected to aheat transfer printing step but through which it can be passed when theheat transfer printing step is carried out.

17. The heat transfer printing sheet of claim 1, wherein the oxidiaingagent acts to sufficiently increase the heat transferable property ofthe basic dye at a temperature of from about to 250C.

18. The heat transfer printing sheet of claim 17, wherein said heatingis conducted under a pressure of from about 50 g/cm to 20 kg/cm

1. A HEAT TRANSFER PRINTING SHEET COMPRISING A BASE SUPPORT SHEET HAVINGFORMED THEREON A PATTERN COMPRISING A BASIC DYE HAVING A POOR HEATTRANSFERABLE PROPERTY, AND OXIDIZING AGENT WHICH IS CAPABLE OFSUFFICIENTLY INCREASING THE HEAT TRANSFERABLE PROPERTY OF THE BASIC DYEWHEN SUBJECTED TO HEATING DURING CONTACT WITH A MATERIAL TO WHICH THEPATTERN IS TO BE TRANSFER-PRINTED SO THAT ONLY THE BASIC DYE CAN BETRANSFERRED TO SAID MATERIAL, AND A BINDER.
 2. The heat transferprinting sheet of claim 1, wherein the pattern comprises an underlayercomprising the basic dye and the binder and an overlayer comprising theoxidizing agent and the binder.
 3. The heat transfer printing sheet ofclaim 1, wherein the pattern comprises an underlayer comprising theoxidizing agent and the binder and an overlayer comprising the basic dyeand the binder.
 4. The heat transfer printing sheet of claim 1, whereinthe base support sheet comprises a material selected from the groupconsisting of paper, converted paper, cellophane, synthetic resin films,metal foils and plates and laminates thereof.
 5. The heat transferprinting sheet of claim 1, wherein the base support sheet is made of amaterial having a thermal resistance property.
 6. The heat transferprinting sheet of claim 1, wherein the basic dye is selected from thegroup consisting of methine (cyanine) basic dyes and cationic dyes,diphenylmethane basic dyes and cationic dyes, triphenylmethane basicdyes and cationic dyes, xanthene basic dyes and cationic dyes, acridinebasic dyes and cationic dyes, quinoneimine basic dyes and cationic dyes,anthraquinone basic dyes and cationic dyes containing a quarternaryamine.
 7. The heat transfer printing sheet of claim 6, wherein the basicdye is selected from the group consisting of Aizen Cathilon Yellow 3GLH(C.I. 48055), Aizen Cathilon Red 6BH (C.I. 48020), Malachite Green (C.I.42000), Crystal Violet (C.I. 42555), Aizen Cathilon Blue 5G (C.I.51005), Aizen Basic Cyanine 6GH (C.I. 42025), Aizen Methylene Blue FZ(C.I. 52015), Aizen Cathilon Brilliant Yellow 5GLH (C.I. Basic yellow13), Aizen Cathilon Orange RH (C.I. 48040) and Astrazon Pink FG (C.I.48015).
 8. The heat transfer printing sheet of claim 1, wherein theoxidizing agent is selected from the group consisting of permanganicacid and permanganate salts therEof; chromic acid and chromate,dichromate and chloride salts thereof; hydrogen peroxide; and alkalimetal and alkaline earth metal peroxides.
 9. The heat transfer printingsheet of claim 8, wherein said ozidizing agent is selected from thegroup consisting of permanganic acid, potassium permanganate, sodiumpermanganate, chromic acid, potassium chromate, potassium dichromate,sodium chromate, ammonium chromate, sodium dichromate, ammoniumdichromate, magnesium chromate, calcium chromate, potassium chromate,chromyl chloride, hydrogen peroxide and sodium, barium and calciumperoxides.
 10. The heat transfer printing sheet of claim 1, wherein thebinder is selected from the group consisting of methylcellulose,ethylcellulose, carboxymethylcellulose, cellulose acetate, cellulosebutyrate, sodium alginate, polyvinyl alcohol, polyvinyl butyral acrylateresins, polyvinyl pyrrolidone, polyvinyl methyl ether, starch, gumarabic, gum tragacanth and gelatin.
 11. The heat transfer printing sheetof claim 1, wherein a resin film through which the basic dye cannot bepassed unless it is subjected to a heat transfer printing step butthrough which it can be passed when the heat transfer printing step iscarried out is disposed on said pattern.
 12. The heat transfer printingsheet of claim 11, wherein said resin is water-soluble and is selectedfrom the group consisting of polyvinyl alcohol, sodium polyacrylate andpolyvinyl pyrrolidone.
 13. The heat transfer printing sheet of claim 11,wherein said resin is oil-soluble and is selected from the groupconsisting of xylene resins, rosin-modified phenol resins, polyvinylbutyral epoxy resins, polystyrene and petroleum resins.
 14. The heattransfer printing sheet of claim 11, wherein said resin film is alaminated film consisting of at least two different resin films.
 15. Theheat transfer printing sheet of claim 1, wherein the base support sheetis preliminarily coated with a resin film through which the basic dyecannot be passed unless it is subjected to a heat transfer printingstep.
 16. The heat transfer printing sheet of claim 1, wherein the basesupport sheet is preliminarily coated with a resin film through whichthe basic dye cannot be passed unless it is subjected to a heat transferprinting step and also wherein the pattern is coated with a resin filmthrough which the basic dye cannot be passed unless it is subjected to aheat transfer printing step but through which it can be passed when theheat transfer printing step is carried out.
 17. The heat transferprinting sheet of claim 1, wherein the oxidiaing agent acts tosufficiently increase the heat transferable property of the basic dye ata temperature of from about 80* to 250*C.
 18. The heat transfer printingsheet of claim 17, wherein said heating is conducted under a pressure offrom about 50 g/cm2 to 20 kg/cm2.